Page 148 - 《精细化工》2020年第3期
P. 148

·566·                             精细化工   FINE CHEMICALS                                  第 37 卷

                 由图 3 可知，反应进行 1  h 时，化合物Ⅴ转化                    红素合成工艺提供了一定的理论基础，也为合成其
            率和化合物Ⅵ选择性分别为 69.1%和 63.5%，延长                       他类胡萝卜素提供了一些新的思路。
            反应时间，化合物Ⅴ转化率和产物Ⅵ选择性随之提
                                                               参考文献：
            高，当反应时间为 3  h 时，化合物Ⅴ转化率和化合
                                                               [1]   STAHL  W,  SIES  H.  Antioxidant  activity  of  carotenoids[J].
            物Ⅵ的选择性分别提高至 83.1%和 70.4%，之后随                           Molecular Aspects of Medicine, 2003, 24(6): 345-351.
            着时间的延长，化合物Ⅴ转化率趋于稳定，但化合                             [2]   BI S Y,  LI  L,  GU H,  et al.  Lycopene  upregulates  ZO-1  and
                                                                   downregulates claudin-1 through autophagy inhibition in the human
            物Ⅵ选择性却略有降低，可能是由于在反应后期，                                 cutaneous squamous cell carcinoma cell line COLO-16[J]. Journal of
                                                                   Cancer, 2019, 10(2): 510-521.
            会存在化合物Ⅵ和阿朴-12′-番茄红素醛的竞争反                           [3]   MARIANI S, LIONETTO L, CAVALLARI M, et al. Low prostate
            应，随着时间的增加，这种竞争会增强，导致化合                                 concentration of lycopene is associated with development of prostate
                                                                   cancer  in  patients  with  high-grade  prostatic  intraepithelial  neoplasia[J].
            物Ⅵ的选择性降低，所以，反应时间控制在 3  h 比                             International Journal of Molecular Sciences, 2014, 15(1): 1433-1440.
            较适宜。                                               [4]   CARIS-VEYRAT C, GARCIA A L, REYNAUD E, et al. A review
                                                                   about  lycopene-induced  nuclear  hormone  receptor  signalling  in
            2.2.3    反应温度对合成化合物Ⅵ的影响                                inflammation  and  lipid  metabolism  via  still  unknown  endogenous
                                                                   Apo-10'-Lycopenoids[J].  International  Journal  for  Vitamin  and
                 当 THF 与 DMSO 的混合溶液〔 V(THF)∶                       Nutrition Research, 2016, 86(1/2): 62-70.
            V(DMSO)=8∶1〕为溶剂，叔丁醇钾为碱性催化剂，                        [5]   PETYAEV I M, DOVGALEVSKY P Y, KLOCHKOV V A, et al.
                                                                   Effect of lycopene supplementation on cardiovascular parameters and
            n(Ⅴ)∶n(Ⅳ)∶n(叔丁醇钾)=1∶2.2∶2.6，反应时间                       markers  of  inflammation  and  oxidation  in  patients  with  coronary
            为 3 h，分别测定反应温度为 20、30、40、50 ℃时化                        vascular disease[J]. Food Science and Nutrition, 2018, 6(6): 1770-1777.
                                                               [6]   COSTA-RODRIGUES  J,  PINHO  O,  MONTEIRO  P  R  R.  Can
            合物Ⅴ的转化率和化合物Ⅵ的选择性，结果见表 3。                               lycopene be considered an effective protection against cardiovascular
                                                                   disease?[J]. Food Chemistry, 2018, 245: 1148-1153.

            表 3    反应温度对化合物Ⅴ转化率和化合物Ⅵ选择性的                       [7]   STAHL W, HEINRICH U, AUST O, et al. Lycopene-rich products
                                                                   and  dietary  photoprotection[J].  Photochemistry  and  Photobiology,
                  影响                                               2006, 5(2): 238-242.
            Table 3    Effect  of  reaction  temperature  on  the  conversion   [8]   URBONAVIČIENĖ D, BOBINAITĖ R, TRUMBECKAITĖ S, et al.
                                                                   Agro- industrial tomato by-products and extraction of functional food
                    of compound  Ⅴ  and the selectivity of compound  Ⅵ   ingredients[J]. Zemdirbyste-Agriculture, 2018, 105(1): 63-70.
                                        反应温度/℃                 [9]   MARTINEZ-CAMARA S, RUBIO S, DEL RIO H, et al. Lycopene
                                                                   production by mated fermentation of blakeslea trispora[J]. Methods
                                  20    30     40     50           in Molecular Biology, 2018, 1852(15): 257-268.
                                                               [10]  CHEN  Yao  (陈瑶).  Research  progress  of  lycopene  production[J].
            化合物Ⅴ转化率/%            81.5   83.1   83.8   84.9         Chemical  Engineering  Design  Communications  (化工设计通讯),
            化合物Ⅵ选择性/%            67.5   70.4   64.2   57.4         2016, 42(12): 58, 62.
                                                               [11]  MEYER K. Method for the manufacture of carotinoids and the novel
                                                                   intermediates: US5166445A[P]. 1992-11-24.
                 如表 3 所示，当反应温度为 30  ℃时，化合物                     [12]  WEGNER  C,  JOHN  M.  Process  for  preparing  phosphonium  salts:
            Ⅵ的选择性最高，为 70.4%。随着温度的升高，能                              US6423873B1[P]. 2002-07-23.
                                                               [13]  ZHANG Xibo (张希波), LIU Honghai (刘洪海), ZHANG Xiaoli (张
            量增加从而更容易越过反应壁垒，加快反应速率，                                 晓丽 ),  et al.  Advanced  in  research  for  chemical  synthesis  of
            化合物Ⅴ的转化率增高；而温度过高时，由于强碱                                 lycopene[J].  Northwest  Pharmaceutical  Journal  (西北药学杂志),
                                                                   2009, 24(1): 78-80.
            和醛的存在，容易引起 Cannizzaro 歧化反应，生成                      [14]  ZHANG  Zhaogui  (张招贵).  Fine  organic  synthesis  and  design[M].
                                                                   Beijing: Chemical Industry Press (化学工业出版社), 2003: 526.
            相应的醇类副产物和羧酸类副产物，导致化合物Ⅵ                             [15]  BABLER  J  H,  POSVIC  H  W.  C-15  phosphonate  reagent
            选择性降低      [22] ，所以，反应温度选择为 30 ℃。                      compositions  for  the  manufacture  of  compounds  such  as  lycopene
                                                                   and methods of synthesizing the same: US5973179A[P]. 1999-10-26.
                                                               [16]  SHEN  R  P, JIANG X Y,  YE W D,  et al.  A  novel  and  practical
            3   结论                                                 synthetic  route  for  the  total  synthesis  of  lycopene[J].  Tetrahedron,
                                                                   2011, 67(31): 5610-5614.
                                                               [17]  MA  Wenxin  (马文鑫),  LIANG  Zhiping  (梁智平),  WANG  Weijun
                 本文以假性紫罗兰酮一步合成 2,6,10-三甲基-                         (王渭军),  et al.  Total  synthesis  of  lycopene[J].  Journal  of  China
            3,5,9-十一烷三烯-1-醛，然后经过 Wittig-Horner 反                   Pharmaceutical  University  (中国药 科大学 学报),  2013,  44(5):
                                                                   390-393.
            应获得 C15 膦酸酯，最终与 2,7-二甲基-2,4,6-辛三                   [18]  SONG  X  H,  XU  H  T,  YE  W  D,  et al.  Practical  synthesis  of
            烯-1,8-二醛通过 Wittig-Horner 反应、转位异构制备                     lycopene[J].  Organic  Preparations  and  Procedures  International,
                                                                   2016, 48(4): 350-354.
            全反式番茄红素。与现有的工艺相比，本文设计了                             [19]  PACE  V,  CASTOLDI  L,  MAZZEO  E,  et al.  Efficient  access  to
                                                                   all-carbon  quaternary  and  tertiary  α-functionalized  homoallyl-type
            以 Wittig-Horner 反应为特征的合成路线，避免了使                        aldehydes  from  ketones[J].  Angewandte  Chemie  International
            用 Wittig 反应导致的副产物不易分离的问题；反应                            Edition, 2017, 56(41): 12677-12682.
                                                               [20]  LI Wei (李伟), DING Xiaolin (丁霄霖), DAI Qingping (戴庆平), et
            中使用的假性紫罗兰酮与 2,7-二甲基-2,4,6-辛三烯                          al.  Purity  determination  of  lycopene  by  different  scanning
            -1,8-二醛是在类胡萝卜素工业生产中普遍应用的化                              calorimetry[J]. Food Science (食品科学), 2002, 23(9): 87-89.
                                                               [21]  ZHANG Wei (张玮), LEI Awang (雷阿旺), ZHAO Zhili (赵志利).
            工中间体，原料来源广泛；通过 3 步反应合成番茄                               Synthesis of Pseudoionones over solid base catalysts[J]. Guangzhou
            红素，反应步骤短，反应总产率为 37.0%，具有一                              Chemical Industry (广州化工), 2010, 38(5): 157-158, 162.
                                                               [22]  HAN Liying (韩丽颖), LI Xianggao (李祥高), WANG Shirong (王
            定的工业化潜力。应用一种 α-取代-α,β-不饱和醛的                            世荣), et al. Synthesis optimization and optoelectronic properties of
                                                                   4-(2,2-diphenylethenyl)-N,  N-bis[(4-methyl)-phenyl]  anilin[J].  Fine
            制备方法于番茄红素的合成中，为简化与改良番茄                                 Chemicals (精细化工), 2013, 30(10): 1096-1101.
   143   144   145   146   147   148   149   150   151   152   153